Derivatized highly branched polysaccharide and a mix for production of polyurethane thereof

ABSTRACT

The invention relates to a highly branched polysaccharide which is derivatized to provide a hydrophobicity which renders it compatible with a polyether polyol with which the underivatized polysaccharide is incompatible. Further the invention relates to a mix for the production of polyurethane. The mix comprises a mixture of the derivatized polysaccharide and a polyether polyol. The polysaccharide of the mix is derivatized to provide a hydrophobicity which renders it compatible with a polyether polyol with which the underivatized polysaccharide is incompatible. The derivatized highly branched polysaccharide used in the invention has an active hydrogen functionality of at least 15 and comprises randomly bonded glucopyranose units, having an average number of 10-100 glucose residues.

This application claims priority Under 35 U.S.C §119(e) of U.S.provisional patent application Ser. No. 60/618,958, entitled “FoamedIsocyanate-based Polymer, a Mix and Process for Production Thereof”,filed Oct. 15, 2004, the complete disclosure of which is herebyincorporated by reference for all purposes.

The invention relates to a highly branched polysaccharide which isderivatized to provide a hydrophobicity which renders it compatible witha polyether polyol with which the underivatized polysaccharide isincompatible. Further the invention relates to a mix for the productionof polyurethane. The mix comprises a mixture of the derivatizedpolysaccharide and a polyether polyol. The polysaccharide of the mix isderivatized to provide a hydrophobicity which renders it compatible witha polyether polyol with which the underivatized polysaccharide isincompatible. The derivatized highly branched polysaccharide used in theinvention has an active hydrogen functionality of at least 15 andcomprises randomly bonded glucopyranose units, having an average numberof 10-100 glucose residues.

BACKGROUND OF THE INVENTION

Polysaccharides can be used in polyurethanes which are prepared byreacting an organic isocyanate with a polyol in the presence ofadditional components like catalysts, surfactants etc. When preparingpolyurethane foams a blowing agent is usually added.

Carbohydrates are known as initiators in the production of polyetherpolyols or as direct additives to a polyol or blend of polyols as partof the polyurethane formulation. Simple carbohydrates such as sucrose,sorbitol, fructose and glucose have been used to initiate polyetherpolyols designed to facilitate solely water blown rigid foams asdescribed in U.S. Pat. No. 5,690,855. U.S. Pat. No. 5,185,383 useshexoses as a polyol starter and U.S. Pat. No. 4,943,597 describes apolyol composition wherein simple carbohydrates such as dextrose,sorbitol, sucrose, alpha-methylglucoside and alpha-hydroxyethylglucosideare suitable initiators for a high molecular weight, high functionalitypolyol which can be used to make substantially water-blown rigid foams.

More complex carbohydrate units such as cellulose and starches have alsobeen employed in the production of polyurethanes as described in U.S.Pat. No. 4,520,139. Complex carbohydrate units such as pectins, starchor other amylaceous materials may be used in foaming systems with orwithout an auxiliary blowing agent. The starches may be modified priorto use. Thus in U.S. Pat. No. 4,401,772 methyl glucoside is formed by anacid catalyzed reaction with starch. This is then reacted with asuitable amine and an alkylene oxide to form a polyether polyol. Morerecently a jet-cooked starch oil composite has been used in conjunctionwith low molecular weight glycol polyol to make a polyurethane foam withaltered characteristics, as described in R. L. Cunningham, et al. J.Appl. Polym. Sci. 69: 957, 1998. Unmodified cellulose and starches, andpolysaccharides have also been converted to polyurethane precursors byalkoxylation and more specifically propoxylation. Formation of polyetherpolyols resulted in compounds useful as precursors for fat mimetics inU.S. Pat. No. 5,273,772, and in rigid and flexible polyurethanes foamsin U.S. Pat. No. 4,585,858. In the process of U.S. Pat. No. 5,273,772,involving carbohydrates capable of having more complex, highly branchedand random glucosidic linkages, water must be rigorously removed priorto alkoxylation. The composition of U.S. Pat. No. 4,585,858 can tolerateabout 15-23% water when crude starch is one of the initiators, howeverthe document specifically refers to starch—meaning compounds with 1,4glucosidic linkages derived from any vegetable source with and withoutchemical modification.

As direct additives untreated carbohydrates have been incorporated intopolyurethane foams in two ways—1) as a partial or complete replacementfor the polyol component, and 2) as an unreacted additive or filler. Thecarbohydrate can be introduced into the foam starting materials eitheras a solution or as a fine solid. When added as a solution, the hydroxylgroups on the carbohydrate can react with the isocyanate component andbecome chemically incorporated into the structure of the polyurethane.Examples of carbohydrates include certain starches, corn syrup,cellulose, pectin as described in U.S. Pat. No. 4,520,139, mono- anddisaccharides as described in U.S. RE31,757, U.S. Pat. Nos. 4,400,475,4,404,294, 4,417,998, oligosaccharides as described in U.S. Pat. No.4,404,295 and pregelatinized starch as described in U.S. Pat. No.4,197,372. As a solid dispersion, the carbohydrate may be inert in thepolymerization reaction, but is physically incorporated into the foam.The advantage is lower cost and the ability of the carbohydrates to charupon combustion, preventing further burning and/or dripping of the foamand reducing smoke formation as described in U.S. Pat. Nos. 3,956,202,4,237,182, 4,458,034, 4,520,139, 4,654,375. Starch and cellulose arecommonly used for this purpose. The starch or cellulose may also bechemically modified prior to foam formulation as described in U.S. Pat.Nos. 3,956,202 and 4,458,034. Use of a dendritic macromolecule inisocyanate based foams are described in U.S. Pat. No. 5,418,301, WO02/10189 and US Applications US 2003/0236315 and US 2003/0236316 and theuse of highly branched polysaccharides are described in U.S. applicationSer. No. 10/854,595.

One structure of a highly branched polysaccharide is shown below.

Normally highly branched polysaccharides have a relatively poorsolubility in polyether polyols having a hydroxyl value of said highlybranched polysaccharides at high active hydrogen functionality andmolecular weight. Accordingly, it would be highly desirable to haveconvenient means for incorporation of highly branched polysaccharides ina polyurethane foam matrix. More particularly, it would be veryadvantageous to be able to incorporate into the polyurethane foam matrixa highly branched polysaccharide having a high active hydrogenfunctionality and which may be readily processed in a polyurethane foamproduction facility.

It is an object of the present invention to provide novel highlybranched polysaccharides which obviate or mitigate at least one of theabove-mentioned disadvantages of the prior art.

It should be noted that all documents cited in this text (“herein citeddocuments”) as well as each document or reference cited in each of theherein-cited documents, and all manufacturer's literature,specifications, instructions, product data sheets, material data sheets,and the like, as to the product mentioned in this text, are herebyexpressly incorporated herein by reference.

SUMMARY OF THE INVENTION

The present invention relates to a highly branched polysaccharidederivatized to provide a hydrophobicity which renders it compatible witha polyether polyol with which the underivatized polysaccharides areincompatible. The polysaccharide comprises of randomly bondedglucopyranose units, having an average number of 10-100 glucose residuesand the derivatized polysaccharide has an active hydrogen functionalityof 15 or more. The glycosidic bonds of the polysaccharide may be alphaor beta and may consist of any of the possible combinations, 1,2 to 1,6;2,1 to 2, 6; etc.

The invention also relates to a mix for the production of apolyurethane. The mix comprises a polyether polyol, a highly branchedpolysaccharide of randomly bonded glucopyranose units, having an averagenumber of 10-100 glucose residues, wherein said polysaccharide has anactive hydrogen functionality of at least 15 and is derivatized toprovide a hydrophobicity which renders it compatible with said polyetherpolyol with which the underivatized polysaccharide is incompatible. Themix may further comprise a blowing agent, at least one catalyst and atleast one surfactant.

A polyurethane may be formed by the reaction between the mix containingisocyanate-reactive hydrogens, and an isocyanate chosen from the classof readily available isocyanato aromatic compounds.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have surprisingly found that highly branchedpolysaccharides are suitably modified to increase their hydrophobiccharacter, and thereby their compatibility with polyether polyols. Thesederivatized highly branched polysaccharides in polyurethane formulationsprovide advantageous load building characteristics in high density andin foamed isocyanate-based polymers. They may be used to partially or tofully displace the conventional copolymer polyols used.

Accordingly, the present invention discloses a novel group ofderivatized highly branched polysaccharides which may be convenientlyincorporated in polyurethane foams. The novel group of derivatizedhighly branched polysaccharides confer significant load buildingproperties to a polyurethane foam matrix and may be used for thispurpose to partially or fully displace current relatively expensivechemical systems which are used to confer load building characteristicsto polyurethane foams.

A feature of the present derivatized highly branched polysaccharide isthat at least 5% by weight of the derivatized highly branchedpolysaccharide may be mixed with a polyether polyol having a hydroxylvalue of 60 or less to form a stable, i.e. uniform liquid at 23° C.

Unless otherwise specified, the terms used in the present specificationand claims shall have the following meanings.

The term “highly branched” when used to describe the polysaccharide ofthe invention refers to a polysaccharide which has at least some doublyor triply branched units. A glucopyranose unit which has three linkagesis a doubly branched unit and a unit which has four linkages is a triplybranched unit. The area (%) of double and/or triple branches in alinkage analysis of the polysaccharide is preferably 0.5-10%, morepreferably 1-7% and most preferably 2-5%. Specific examples of suchhighly branched polysaccharides comprise polydextrose and apolysaccharide produced from starch in a heat treatment process known aspyroconversion. The highly branched polysaccharide of the invention mayfurther be alkoxylated.

The term “functionality” of the derivatized highly branchedpolysaccharide and its derivative is dependent upon the average numberof glucose residues and refers to the number active hydroxyl groups permolecule. For the purposes of “functionality,” the polysaccharidemolecule is defined as low-monomer polysaccharide. Normally in a strictsense functionality refers to the number of isocyanate-reactivehydrogens on molecules in the polyol side of the formulation.

The term “polydextrose” as used herein refers to one example of a highlybranched polysaccharide. It includes polymer products of glucose whichare prepared from glucose, maltose, oligomers of glucose or hydrolyzatesof starch, which are polymerized by heat treatment in a polycondensationreaction in the presence of an acid e.g. Lewis acid, inorganic ororganic acid, including monocarboxylic acid, dicarboxylic acid andpolycarboxylic acid, such as, but not limited to the products preparedby the processes described in the following U.S. Pat. Nos. 2,436,967,2,719,179, 4,965,354, 3,766,165, 5,051,500, 5,424,418, 5,378,491,5,645,647 5,773,604, or 6,475,552, the contents of all of which areincorporated herein by reference.

The term polydextrose also includes those polymer products of glucoseprepared by the polycondensation of glucose, maltose, oligomers ofglucose or starch hydrolyzates described hereinabove in the presence ofa sugar alcohol, e.g. polyol, such as in the reactions described in U.S.Pat. No. 3,766,165. Moreover, the term polydextrose includes the glucosepolymers, which have been purified by techniques described in prior art,including any and all of the following but not limited to (a)neutralization of any acid associated therewith by base additionthereto, or by passing a concentrated aqueous solution of thepolydextrose through an adsorbent resin, a weakly basic ion exchangeresin, a type II strongly basic ion-exchange resin, mixed bed resincomprising a basic ion exchange resin, or a cation exchange resin, asdescribed in U.S. Pat. Nos. 5,667,593 and 5,645,647, the contents ofwhich are incorporated by reference; or (b) decolorizing by contactingthe polydextrose with activated carbon or charcoal, by slurrying or bypassing the solution through a bed of solid adsorbent or by bleachingwith sodium chlorite, hydrogen peroxide and the like; (c) molecularsieving methods, like UF, RO (reverse osmosis), size exclusion, and thelike; (d) or enzymatically treated polydextrose or (e) any otherrecognized techniques known in the art. Among the purification processesused in the art the following may be especially mentioned: bleaching,e.g. using hydrogen peroxide as described in U.S. Pat. No. 4,622,233;membrane technology as described in U.S. Pat. No. 4,956,458; ionexchange e.g. removal of citric acid as described in U.S. Pat. No.5,645,647 or removal of color/bitter taste as described in U.S. Pat. No.5,091,015; chromatographic separation, with a strong cation exchanger asdescribed in WO92/12179; hydrogenation, in combination with ion exchangeas described in U.S. Pat. No. 5,601,863; U.S. Pat. No. 5,573,794 or withion exchange and chromatographic separation as described in U.S. Pat.No. 5,424,418; or solvent extraction as described in U.S. Pat. No.4,948,596; EP 289 461, the contents of said patents being incorporatedby reference.

Moreover, the term polydextrose includes hydrogenated polydextrose,which, as used herein, includes hydrogenated or reduced polyglucoseproducts prepared by techniques known to one of ordinary skill in theart. Some of the techniques are described in U.S. Pat. Nos. 5,601,863,5,620,871 and 5,424,418, the contents of which are incorporated byreference. The term polydextrose also encompasses fractionatedpolydextrose which is a conventional, known material and can be producede.g. by the processes disclosed in U.S. Pat. Nos. 5,424,418 and4,948,596 the contents of which are incorporated by reference.

Polydextrose is commercially available from companies such as DaniscoSweeteners, Staley and Shin Dong Bang. Purified forms of polydextroseare marketed by Danisco Sweeteners under the name Litesse® or Litesse®II and by Staley under the name Stalite® III. A reduced form of Litesse®is called Litesse® Ultra. The specifications of the Litesse®polydextrose products are available from Danisco Sweeteners.

A further highly branched polysaccharide is derived by pyroconversionfrom starch. Starch is made of glucose molecules attached by α-(1,4)bonds, with some branching by means of α-(1,6) bonds. The degree ofbranching depends on the source of the starch. The polysaccharide isproduced from starch in a heat treatment process known aspyroconversion. Pyrodextrins are starch hydrolysis products obtained ina dry roasting process either using starch alone or with trace levels ofacid catalyst. The first product formed in this reaction is solublestarch, which in turn hydrolyzes further to form dextrins. The molecularweight of the final product depends on the temperature and duration ofheating. Transglucosidation can occur in the dextrinization process, inwhich rupture of an α-(1,4) glucosidic bond is immediately followed bycombination of the resultant fragments with neighboring hydroxyl groupsto produce new linkages and branched structures. Thus, a portion of theglycosidic bonds are scrambled. A commercially available pyroconvertedstarch is called Fibersol-2® and is available from Matsutani America,Inc.

As used throughout this specification, the term “compatible”, when usedin connection with the solubility characteristics of the derivatizedhighly branched polysaccharide, it is intended to mean that the liquidformed upon mixing the derivatized highly branched polysaccharide andthe polyether polyol does not cause precipitation and thus is uniformand stable. Further the formed liquid has a substantially constant lighttransmittance (transparent at one extreme and opaque at the otherextreme) for at least 2 hours, preferably at least 30 days, morepreferably a number of months, after production of the mixture. Indifferent embodiments, the stable liquid will be in the form of a clear,homogeneous liquid (e.g., a solution) which will remain as such overtime or in the form of an emulsion of the derivatized highly branchedpolysaccharide in the polyol which will remain as such over time—i.e.the polysaccharide will not settle out over time. The polarity maymoreover be reflected by a term known as the solubility parameter (δ), avalue which for the very polar water is 23.4 and decreases as one movesto very non polar solvents as methyl t-butyl ether, for which thesolubility parameter is 7.4. A polymer with a solubility parametersimilar to the solvent will dissolve in it. Components with dramaticdifferences in solubility parameters, for example water and oil—will notdissolve.

The term “compatibility indicating mixture” refers to a mixture of thederivatized highly branched polysaccharide and a polyether polyol, whichforms a uniform liquid at 23° C. The hydrophobicity of the derivatizedhighly branched polysaccharide is sufficient to provide a uniform liquidmixture although the underivatized polysaccharide is incompatible withthe polyether polyol, i.e. does not form a uniform liquid mixture in thesame conditions.

The term “load efficiency”, as used throughout this specification,indicates the ability of the derivatized highly branched polysaccharideto generate firmness in an isocyanate based foam matrix. The efficiencyis defined as the number of Newtons of foam hardness increase per % ofthe derivatized highly branched polysaccharide in the resin blend.Typically, foam firmness is described using Indentation Force Deflection(IPD) at 50% deflection or Compressive Load Deflection (CLD) at 50%deflection, measured pursuant to ASTM D3574. An IFD number representsthe pounds of force required to indent a foam sample by a specifiedpercentage of its original thickness. The CLD values are given in poundsper square inch (psi). The force in pounds needed to compress the sampleis recorded and the result is reported in psi by dividing the force bythe surface area of the sample.

The term “index” refers to the ratio of isocyanate groups of theisocyanate and hydroxyl groups of the polyol composition [NCO/OH].

The term “polyurethane” is used both when urethanes and isocyanuratesare included. For the purposes of this invention no special distinctionis made between polyurethanes and polyisocyanurates.

In the specification and the claims the term “adding an organicisocyanate to a polyol composition” includes combining the twocomponents irrespectively of which is added to which in connection withthe process of the present invention.

The derivatized highly branched polysaccharide of the inventioncomprises randomly bonded glucopyranose units and has an average numberof 10-100 glucose residues. Moreover the polysaccharide has an activehydrogen functionality of at least 15, preferably 15 to 70, morepreferably 20 to 60, most preferably 30 to 50. The polysaccharide isderivatized to provide a hydrophobicity which renders it compatible witha polyether polyol with which the underivatized polysaccharide isincompatible.

There are a number of ways to increase the hydrophobic character ofthese highly branched polysaccharides. For example, anoctenylsuccinylation may be carried out as described in U.S. Pat. Nos.4,035,235; 5,672,699; or 6,037,466. However, a preferred approach isesterification with a fatty acid, preferably containing 6 to 12 carbonatoms. Methods for esterifying similar structures such as starch aredescribed in U.S. Pat. Nos. 2,461,139; 4,720,544; 5,360,845; 6,455,512;and 6,495,679. Methods for esterifying other polysaccharides aredisclosed in U.S. Pat. Nos. 4,517,360; 4,518,772; 5,589,577; 5,840,883;5,977,348; and 6,706,877.

There are several different synthetic routes described in prior art.Modifying starch with solvents are described in U.S. Pat. Nos.5,589,577, 5,681,948, 5,840,883 and 6,495, 679. Methods for producingalkyl ester derivatives of sucrose, which reactions require no solventand are carried out under vacuum in the melt are described in U.S. Pat.Nos. 4,517,360, 4,518,772, 5,585,506, 5,681,948, 5,767,257, 5,945,519,6,080,853, 6,121,440, 6,303,777, 6,620.952 and 6,706,877. Anotherderivatization procedure described in 4,011,389, 4,223,129, 4,720,544,4,950,743, 5,886,161, 6,100,391 and 6,204,369 covers the reaction of along chain alcohol directly with the polysaccharide producing glucosidestructure. A process where the same number of hydroxyl groups remains inthe final product and where a long chain a olefin epoxide monomer in thepresence of base is added to polyols to introduce the desiredhydrophobicity is described in U.S. Pat. Nos. 3,932,532 and 4,011,389.Processes where water is present are described in U.S. Pat. Nos.2,461,139, 3,318,868, 4,720,544, 5,360,845, 6,011,092, 6,455,512 and6,605,715. A process for modifying carbohydrates which utilizesepichlorohydrin which is reacted with a long chain alcohol in thepresence of a Lewis acid catalyst and after neutralization, and were theproduct is added to a polyglycerol which has been converted to itsalkoxide is described in U.S. Pat. No. 4,086,279. Moreover a process foresterification of starch where high boiling solvents such as DMF or DMSOare replaced by supercritical CO₂ is described in U.S. Pat. No.5,977,348.

A particularly straight forward method is comprised of the steps of:mixing a highly branched polysaccharide with a suitable ether oraromatic hydrocarbon solvent, such as tetrahydrofuran, diethylene glycoldimethyl ether, xylene or toluene; adding a base, such as NaOH or KOH;and, then the carboxylic acid. The reaction is driven to completion withheat and at the same time removing water.

Alternatively, the hydrophobe imparting carboxylic acid moiety can beadded during or near the completion of the polysaccharide preparationreaction.

As described above the preferred polysaccharide composition utilized inthe process for preparing a polyurethane comprises a derivatized highlybranched polysaccharide of randomly bonded glucopyranose units having anaverage number of 10-100 glucose residues. The preferred weight of fattyacid residues is 5 to 50%, preferably 15 to 40% based on the weight ofthe final a derivatized highly branched polysaccharide.

The hydrophobicity of the derivatized highly branched polysaccharide issufficient to cause a mixture of said polysaccharide and said polyetherpolyol with which the underivatized polysaccharide is incompatible. Thiscompatibility indicating mixture comprises at least 5% (w/w) of saidpolysaccharide and still forms a uniform liquid at 23° C. Preferably thecompatibility indicating mixture comprises 5 to 50%, more preferably 5to 40%, most preferably 5 to 30% of the polysaccharide and still forms auniform liquid at 23° C.

In one embodiment of the invention the polysaccharide is derivatized bya chemical reaction with a hydrophobic organic compound comprising-6-20carbon atoms selected from aliphatic and aromatic carbon atoms andcombinations thereof. More in detail; the organic compound is selectedfrom C₆-C₁₂ carboxylic acids and C₆-C₁₂ organic alcohols. In a preferredembodiment the carboxylic acid is selected from fatty acids or reactivederivatives thereof. The organic alcohols can be selected from diols andmonols, preferably containing at least one primary hydroxyl group.

In a preferred embodiment ester groups are introduced to thepolysaccharide whereupon the solubility parameter of the polysaccharidederivatives lowers. When the solubility parameter is below 14,preferably below 12 the modified polysaccharide dissolves in solvents inwhich underivatized and less substituted polysaccharide is insoluble.The hydrophilicity decreases and therefore the solubility of thepolysaccharide derivatives in less polar solvents increases as thedegree of substitution increases.

In a preferred embodiment where the polysaccharide is derivatized with afatty acid the weight of fatty acid residues in the derivatizedpolysaccharide is 5 to 50%, more preferably 15 to 40% based on theweight of the derivatized highly branched polysaccharide.

The polyether polyol, with which the underivatized polysaccharide isincompatible may primarily comprise polypropylene oxide, preferably atleast 50% polypropylene oxide, more preferably at least 70%, still morepreferably 70 to 90%, most preferably 75 to 80%. It may preferably havea hydroxyl value of at most 60 mg KOH/g, more preferably 15 to 55 mgKOH/g, most preferably 28 to 36 mg KOH/g.

Further the polyether polyol may have a molecular weight in the range offrom 200 to 12,000, preferably from 2,000 to 7,000, most preferably from2,000 to 6,000.

In one embodiment of the present invention the polysaccharide consistsof randomly cross-linked glucose units with all types of glycosidicbonds, containing minor amounts of a bound sugar alcohol and an acid,and having an average molecular weight between about 1,500 and 18,000.The polysaccharide has predominantly 1,6 glycosidic bonds and is apolycondensation product of glucose, maltose or other simple sugars orglucose-containing material such as hydrolyzed starch and a sugaralcohol in the presence of an acid, preferably a carboxylic acid.

Examples of suitable acids include, but are not limited to mono, di ortri carboxylic acid or their potential anhydrides, such as formic,acetic, benzoic, malonic, fumaric, succinic, adipic, itaconic, citricand the like, and/or a mineral acids, such hydrochloric acid, sulfuricacid, sulfurous acid, thiosulfuric acid, dithionic acid, pyrosulfuricacid, selenic acid, selenious acid, phosphorous acid, hypophosphorousacid, pyrophosphoric acid, polyphosphoric acid, hypophosphoric acid,boric acid, perchloric acid, hypochlorous acid, hydrobromic acid,hydriodic acid and silicic acid; acidic alkali metal or alkaline earthmetal salts of the above acids such as sodium bisulfate and sodiumbisulfite; or mixtures of these acids (and/or acidic alkali or alkalineearth metals salts) with phosphoric acid and the like at about 0.001-3%.The polysaccharide thus produced will contain minor amounts of unreactedsugar alcohol and/or acid and a mixture of anhydroglucoses (reactionintermediates).

In a preferred embodiment the sugar alcohols are selected from the groupconsisting of sorbitol, glycerol, erythritol, xylitol, mannitol,galactitol or mixtures thereof, typically at a level of 5-20% by weight,preferably 5-15%, more preferably 8-12%.

The polysaccharide formed may be further purified or modified by avariety of chemical and physical methods used alone or in combination.These include, but are not limited to: chemical fractionation,extraction with organic solvents, neutralization with a suitable base,purification by chromatography (such as ion exchange or size exclusion),membrane or molecular filtration, further enzyme treatment, carbontreatment and hydrogenation, which is a specific process of reduction.

In the most preferred embodiment of the invention the polysaccharide isa polycondensation product of glucose, sorbitol and citric acid. Thewater soluble polysaccharide is produced by reacting glucose withsorbitol (8-12% by weight) in the presence of citric acid (0.01-1% byweight) under anhydrous melt conditions and reduced pressure. Thepolysaccharide may be purified by ion exchange to produce a form inwhich the acidity is less than 0.004 meq/gm; referred to as low-aciditypolyol. Or, it may be purified by a combination of ion exchange andhydrogenation; referred to as hydrogenated polyol. Upon hydrogenationthe reducing saccharides are typically less than 0.3% of the totalcarbohydrate content. Or, it may be further purified by anion exchangeand molecular filtration to reduce acidity and the concentration ofmonomeric reaction by-products; referred to as low-monomer polyol. Aportion of the water used in processing may be removed to achieve thedesired moisture content. In the low-acidity and hydrogenated forms thepolysaccharide constitutes about 90% of the total carbohydrate content:the remainder consisting of glucose, sorbitol and anhydroglucoses. Inthe low-monomer form the polysaccharide constitutes 99+% of the totalcarbohydrate content. In this most preferred embodiment the highlybranched polysaccharide is a polydextrose.

The water content in all the above mentioned cases may also be adjustedto allow milling as either a coarse or fine powder. The amount of watermay however also define the need of isocyanate. If more water ispresent, the needed amount of isocyanate increases. On the other handthe use of a higher amount of isocyanate may lead to a polyurethane foamwhich is hard and may have a stiff feeling i.e. is “boardy”.

In another embodiment of the invention the polysaccharide haspredominantly beta-1,4 linkages and a varying number of glucose residueswhich are hydrolyzed from starch to form dextrins and subsequentlylinked to form branched structures. In this embodiment thepolysaccharide is preferably pyroconverted starch.

In a preferred embodiment of the invention the derivatized highlybranched polysaccharide is a polydextrose having an active hydrogenfunctionality of at least 15, which is derivatized with a C₈₋₁₂-fattyacid to provide a hydrophobicity which renders it compatible with apolyether polyol with which the underivatized polydextrose isincompatible.

Furthermore the invention relates to a mix for the production of apolyurethane comprising a mixture of a polyether polyol and a highlybranched polysaccharide of randomly bonded glucopyranose units, havingan average number of 10-100 glucose residues. The polysaccharide has anactive hydrogen functionality of at least 15 and is derivatized toprovide a hydrophobicity which renders it compatible with said polyetherpolyol with which the underivatized polysaccharide is incompatible.

In a preferred embodiment the mix comprises 1 to 50%, more preferably 5to 20%, most preferably 10 to 15% by weight of the polysaccharide.

A suitable mix may comprise one or more polyether polyols, copolymerpolyols, blowing agent(s), catalyst(s), surfactant(s) and additives, forexample pigments or fillers or ingredients necessary to achieve adesired property such as flame retardancy, increased durability etc. Thefollowing constituents noted in parts per hundred polyol may be added tothe mix: water (1-30), catalyst (1-10), surfactant (1-25), crosslinkingagent (0-30) and if desired, an auxiliary blowing agent (0-100).

In a preferred embodiment the derivatized highly branched polysaccharideof the present invention is used as a partial or total replacement forcopolymer polyols in high resilient (HR) molded flexible polyurethanefoam applications. High resilient foams are for example used as cushionmaterial in household furnishings and automobiles. The derivatizedhighly branched polysaccharide or mix of the invention may also be usedas a partial or total replacement for copolymer polyols in carpetunderlay and packaging foam applications.

In another preferred embodiment the mix of the invention may in additionto the polyether polyol and the polysaccharide comprise at least onecatalyst and at least one surfactant. The mix of the invention mayfurther comprise at least one blowing agent selected from water,non-water blowing agents, liquid carbon dioxide and combinations thereofand the blowing agent may also comprise water. Preferably the non-waterblowing agents are low-boiling organic liquids, such as acetone, methyl,formate, formic acid, pentane(s), isopentane, n-pentane or cyclopentane,HCFC 141, HFC 245, HFC 365, HFC 134, HFC 227 or a mixture thereof.

Moreover, crosslinking agents, additives like pigments or fillers andother additional components may be added. Although, the derivatizedhighly branched polysaccharide mainly reacts with the isocyanate, insome embodiments of the invention it can also serve as filler.

Any suitable catalyst and surfactant known in the art may be used toobtain the desired characteristics. In a preferred embodiment thecatalyst may be selected from the group consisting of tertiary aminesand metallic salts or mixtures thereof. Amine catalysts can include, butare not limited to methyl morpholine, triethylamine, trimethylamine,triethylenediamine and pentamethyldiethylenetriamine. Metallic salts caninclude, but are not limited to tin or potassium salts such as potassiumoctoate and potassium acetate. A mixture of catalysts is preferred (e.g.Polycat®5, 8,46K; Dabco® K15, 33LV, TMR—all produced by Air Products;Jeffcat® ZF10—produced by Huntsman). In a preferred embodiment thesurfactants may be silicone surfactants used to aid dimensionalstability and uniform cell formation. Examples of suitable siliconesurfactants are the Dabco® series DC5890, DC 5598, DC5043, DC5357 andDC193—all produced by Air Products.

The mixture may further comprise a crosslinking agent selected from thegroup consisting of triethanolamine, glycerin and trimethylol propane.In a preferred embodiment of the invention 1-2% diethanolamine by weightof the mix is added to the mixture. Moreover, additives like pigments orfillers and other additional components may be added.

In a preferred embodiment of the invention the mix comprises a polyetherpolyol and a polysaccharide which is a polydextrose having an activehydrogen functionality of at least 15, derivatized with a C₈₋₁₂-fattyacid to provide a hydrophobicity which renders it compatible with apolyether polyol with which the underivatized polydextrose isincompatible.

The isocyanates in the present invention may come from the class ofreadily available isocyanato aromatic compounds. Depending upon thedesired properties, examples of preferred aromatic isocyanates include2,4 and 2,6 toluene di-isocyanate (TDI) such as that prepared by thephosgenation of toluene diamine produced by the nitration and subsequenthydrogenation of toluene. The TDI may be a mixture of the 2,4 and 2,6isomers in ratios of either 80:20 or 65:35 with the more preferred being80:20 (e.g. TDI 80 produced by Lyondell). Another preferred isocyanateis methylene diphenylisocyanate (MDI) such as prepared by thecondensation of aniline and formaldehyde with subsequent phosgenation.The MDI may be a mixture of 2,4′ and 4,4′methylene diphenyldiisocyanateas well as a mixture of the 2,4 and 4,4 isomers with compounds havingmore than two aromatic rings—polymeric-MDI or PMDI (e.g. Lupranate®M20S—produced by BASF, PAPI®27—produced by Dow and Mondur®MR produced byBayer).

A polyurethane foam may be prepared from the polysaccharide or mix ofthe invention by mixing a polyether polyol and polysaccharide with atleast one surfactant, at least one catalyst and at least one blowingagent selected from water and non-water agents, adding an organicisocyanate and allowing the mixture to foam. Special additives, such asfillers, flame retarding agents, crosslinking agents and agents forincreased durability may be included. Such additives are preferablyadded in amounts which are common in the art and thus well known tothose skilled in the art. However, a special filler of the presentinvention comprises the branched polysaccharide which is included in themix of the invention. The ratio of isocyanate groups of said isocyanateand hydroxyl groups of said polyol is from 1.2:1 to 1:1.2, preferably1.1:1 to 1:1.1. The use of the novel derivatized highly branchedpolysaccharides to partially or fully displace copolymer polyolsconventionally used to confer load building characteristics inisocyanate-based polymer foams, are described in detail in U.S. patentapplication No. U.S. 60/618,958 filed on the same day, in the name ofthe same inventors and with the title “A foamed isocyanate-basedpolymer, a mix and process for production thereof”, the contents ofwhich are hereby incorporated by reference.

The following examples are given to further illustrate the invention andare not intended to limit the scope thereof. Based on the abovedescription a person skilled in the art will be able to modify theinvention in many ways to provide derivatized polysaccharides andpolyurethanes with a wide range of defined properties.

Example 1 discloses preparation of a highly branched polysaccharide andexample 2 solubility of the polysaccharide according to Example 1.Examples 3 to 6 illustrate production and derivatization of highlybranched polysaccharides, Example 7 discloses solubility evaluations ofthe derivatized highly branched polysaccharides of Examples 3 to 6, andExamples 8 to 10 illustrate the use of the derivatized highly branchedpolysaccharide of Example 3 in isocyanate based foam. Examples 11 and 12discloses comparative isocyanate based foams without derivatized highlybranched polysaccharides.

Examples 13 to 15 illustrate three different reactions of polydextroseesters and example 16 discloses production of polydextrose ether.Example 17 discloses solubility evaluations of some of the polydextroseesters of examples 14 and 15. Examples 18-21 discloses comparativeisocyanate based foams without polydextrose and examples 22-27 disclosesthe use of some of the polydextrose esters of example 14 and 15 inisocyanate based foams.

EXAMPLE 1 (COMPARATIVE)

A mixture of 267 grams of dextrose monohydrate (244 gram anhydrousdextrose) and 30 grams of sorbitol is melted and heated under partialvacuum, with stirring, to 130 C., a solution of 0.3 gram of citric acidin 5 milliliters of water is added, the temperature of the mixture isincreased to 152° C., and stirring is continued for 22 minutes underpartial vacuum at 152-188° C. After removing water under vacuum, 252grams of product is obtained. The product has a final hydroxyl number of830. (equivalent wt=68)

The solubility of the highly branched polysaccharides according toExample 1 in a glycerol based polyether polyol with a hydroxyl value of32 mg KOH/g is evaluated.

EXAMPLE 2

15.0 g of respective highly branched polysaccharide according to Example1 is added to a beaker containing 75.0 g of a glycerol based polyetherpolyol with a hydroxyl value of 32 mg KOH/g. The mixture is heated understirring to 120° C. during 30 minutes and then allowed to cool down toroom temperature. The ability for the highly branched polysaccharide toform a stable solution with the polyether polyol is evaluated after 120minutes.

If the highly branched polysaccharides of Examples 1 is unable to form astable solution with the glycerol based polyether polyol of hydroxylvalue 32 mg KOH/g. the highly branched polysaccharide according toExamples 1 partly precipitate from the solution and this can be observedin the form of a separate phase at the bottom of the beaker.

EXAMPLE 3

25 kg of the highly branched polysaccharide according to Example 1, 8.4kg of an aliphatic acid with nine carbon atoms having an acid number of363 mg KOH/g, 0.1 kg KOH and 3.3 kg of xylene are charged to a reactorequipped with a heating system with accurate temperature control, amechanical stirrer a pressure gauge, a vacuum pump, a Dean-Stark devicefor azeotropic removal of water, a cooler, nitrogen inlet and areceiver. The mixture is heated under stirring, with a nitrogen flow of500-600 l/h through the reaction mixture, from room temperature to 170°C. At this temperature all xylene is refluxing and the reaction waterwhich started to form is removed by azeotropic distillation. Thereaction is allowed to continue for a further 12 hours at 170° C., afterwhich the reaction temperature is increased to 180° C. The reactionmixture is kept at this temperature for a further 2.5 hours until anacid value of 6 mg KOH/g is obtained. Full vacuum is then applied to thereactor to remove all xylene from the final product. Approximately 32.4kg of the derivatized, highly branched polysaccharide is obtained andthis product has a hydroxyl value of 545 (equivalent wt=103).

EXAMPLE 4

25 kg of the highly branched polysaccharide according to Example 1, 12kg of an aliphatic acid with nine carbon atoms having an acid number of363 mg KOH/g, 0.1 kg KOH and 3.3 kg of xylene are charged to a reactorequipped with a heating system with accurate temperature control, amechanical stirrer a pressure gauge, a vacuum pump, a Dean-Stark devicefor azeotropic removal of water, a cooler, nitrogen inlet and areceiver. The mixture is heated under stirring, with a nitrogen flow of500-600 l/h through the reaction mixture, from room temperature to 170°C. At this temperature all xylene is refluxing and the reaction waterwhich started to form is removed by azeotropic distillation. Thereaction is allowed to continue for a further 12 hours at 170° C., afterwhich the reaction temperature is increased to 180° C. The reactionmixture is kept at this temperature for a further 2.5 hours until anacid value of 6 mg KOH/g is obtained. Full vacuum is then applied to thereactor to remove all xylene from the final product. Approximately 35.6kg of the derivatized, highly branched polysaccharide is obtained andthis product has a hydroxyl value of 460 (equivalent wt=122).

EXAMPLE 5

A mixture of 267 grams of dextrose monohydrate (244 gram anhydrosedextrose) and 30 grams of sorbitol is melted and heated under partialvacuum, with stirring, to 130 C., a solution of 0.3 gram of citric acidin 5 milliliters of water is added, the temperature of the mixture isincreased to 152 C., and stirring is continued for 22 minutes underpartial vacuum at 152-188 C. Then, 100 g of an aliphatic acid with ninecarbon atoms having an acid number of 363 mg KOH/g, is added and thestirring under partial vacuum at 152-188 C is continued for another 30minutes to remove the water. Approximately 341 grams of the derivatized,highly branched polysaccharide is obtained and this product has ahydroxyl value of 505 (equivalent wt=111).

EXAMPLE 6

A mixture of 267 grams of dextrose monohydrate and 30 grams of sorbitolis melted and heated under partial vacuum, with stirring, to 130 C., asolution of 0.3 gram of citric acid in 5 milliliters of water is added,the temperature of the mixture is increased to 152 C., and stirring iscontinued for 22 minutes under partial vacuum at 152-188 C. Then, 150 gof an aliphatic acid with nine carbon atoms having an acid number of 363mg KOH/g, is added and the stirring under partial vacuum at 152-188 C iscontinued for another 30 minutes. Approximately 385 grams of thederivatized, highly branched polysaccharide is obtained and this producthas a hydroxyl value of 401 (equivalent wt=140).

EXAMPLE 7

The solubility of each of the derivatized highly branchedpolysaccharides according to Examples 3-6 in a glycerol based polyetherpolyol with a hydroxyl value of 32 mg KOH/g is evaluated.

15.0 g of respective derivatized highly branched polysaccharideaccording to Examples 3-6 is added to a beaker containing 75.0 g of aglycerol based polyether polyol with a hydroxyl value of 32 mg KOH/g.The mixture is heated under stirring to 120° C. during 30 minutes andthen allowed to cool down to room temperature. The ability for eachderivatized highly branched polysaccharide to form a stable solutionwith the polyether polyol is evaluated after 120 minutes.

The solubility of the evaluated derivatized highly branchedpolysaccharides according to Example 3-6 in the glycerol based polyetherpolyol is confirmed. If fully transparent solutions, which are stableover time are obtained it shows excellent solubility. Samples of higherconcentrations based on the products obtained according to Examples 3-6are then prepared. These are then evaluated with regard to viscosity at23° C. Samples of different concentrations of derivatized highlybranched polysaccharide according to Examples 3-6 in polyether polyolare prepared and found to be fully compatible with the base glycerolbased polyether polyol if these stable solutions remains as such evenafter 30 days.

EXAMPLES 8-12

Examples 8-12 illustrate the use of the present derivatized highlybranched polysaccharide in a typical isocyanate based high resilient(HR) based foam. In each Example, the isocyanate based foam is preparedby the pre-blending of all resin ingredients including polyols,copolymer polyols (if used), catalysts, water, and surfactants as wellas the derivatized highly branched polysaccharide of interest (if used).The isocyanate is excluded from the mixture. The resin blend andisocyanate are then mixed at an isocyanate index of 100 using aconventional two-stream mixing technique and dispensed into a preheatedmold (65° C.) having the dimensions 38.1×38.1×10.16 cm. The mold is thenclosed and the reaction allowed to proceed until the total volume of themold is filled. After approximately 6 minutes, the isocyanate based foamcan be removed and, after proper conditioning, the properties ofinterest are measured. The methodology will be referred to in Examples8-12 as the General Procedure.

In Examples 8-12, the following materials are used:

E837, base polyol, commercially available from Lyondell;

E850, a 43% solids content copolymer (SAN) polyol, commerciallyavailable from Lyondell;

D-PDX, a derivatized highly branched polysaccharide produced Example 3above;

DEAO LF, diethanol amine, a crosslinking agent commercially availablefrom Air Products;

Glycerine, a crosslinking agent, commercially available from Van Waters& Rogers;

Water, indirect blowing agent;

Dabco 33LV, a gelation catalyst, commercially available from AirProducts;

Niax A-1, a blowing catalyst, commercially available from Witco;

Y-10184, a surfactant, commercially available from Witco;

Lupranate T80, isocyanate (toluene diisocyanate—TDI), commerciallyavailable from BASF.

Unless otherwise stated, all parts reported in Examples 8-12 are inparts by weight.

In Examples 8-12, isocyanate based foams based on the formulations shownin Table 1 are produced using the General procedure referred to above.

In Examples 8-10, isocyanate based foams are prepared in the absence ofany copolymer polyol. The isocyanate based foams are formulated with aH₂O concentration of 3.8% resulting in an approximate foam core densityof 1,9 pcf. The level of derivatized highly branched polysaccharide isvaried from 6.7% to 13.4% by weight in the resin.

The results of physical property testing for each foam is the densityand Indentation Force Deflection (IPD) at 50% deflection, measuredpursuant to ASTM D3574. The introduction of the derivatized highlybranched polysaccharide to the isocyanate based polymer matrix resultsin a greatly improved hardness increase for the foam from Example 8 toExample 9, and for the foam from Example 9 to Example 10. The hardnessis improved with the increase of the amount of derivatized highlybranched polysaccharide.

By this analysis, a “load efficiency” for each foam may be reported andrepresents the ability of the derivatized highly branched polysaccharideto generate firmness in the isocyanate based foam matrix. The efficiencyis defined as the number of Newtons of foam hardness increase per % ofthe derivatized highly branched polysaccharide in the resin blend.

The introduction of the derivatized highly branched polysaccharideresults in a foam hardness increase.

In Examples 11 and 12, isocyanate based foams based on the formulationsshown in Table 1 are produced using the General Procedure referred toabove.

In Examples 11 and 12, isocyanate based foams are prepared in theabsence of any derivatized highly branched polysaccharide. Copolymerpolyol is used to increase foam hardness. Thus, it will be appreciatedthat Examples 11 and 12 are provided for comparative purposes only andare outside the scope of the present invention. The isocyanate basedfoams are formulated with a H₂O concentration of 3.8% resulting in anapproximate foam core density of 1,9 pcf. The level of the copolymerpolyol is varied from 8 to 26% by weight in the resin.

The result of physical property testing for the introduction of thecopolymer results in a foam hardness which however is not as good as forthe foams of Examples 8 to 10. TABLE 1 Examples Ingredient 8 9 10 11 12E837 86.6 83.2 79.9 32.6 74.7 E850 — — — 60.9 18.7 D-PDX 6.7 10.1 13.4 —— DEOA LF 1.0 1.0 1.0 1.0 1.0 glycerin 0.6 0.6 0.6 0.6 0.6 water 3.7 3.73.7 3.7 3.7 Dabco 33LV 0.4 0.4 0.5 0.3 0.3 Niax A-1 0.07 0.07 0.07 0.070.07 DC5169 — — — — — Y10184 0.9 0.9 0.9 0.9 0.9 Total Resin 100.0 100.0100.0 100.0 100.0 Lupranate T80 50.9 53.6 56.3 38.1 38.7 Index 100 100100 100 100 % water 3.8 3.8 3.8 3.8 3.8 % SAN in resin 0 0 0 26 8 % HBPin resin 6.7 10.0 13.4 0 0 Total dry weight (g) 444 440 441 514 519Density (pcf) 1.9 1.9 1.9 1.9 1.9 50% IFD (N) INCREASES -> DECREASES ->% Hysteresis ACCEPTABLE LOW Load Efficiency EXCELLENT ACCEPTABLE

EXAMPLE 13

Polydextrose Ester—Reaction of Polydextrose with a Mixture of MethylEsters

(Theoretical Level of OH Replacement ˜30%)

A mixture of 9.8 g (0.15 mole) of 85% KOH, 80 ml of methanol and 55.8 g(0.3 eq) of CE-1095 (P&G CE-1095—Methyl Decanoate) in a 250 ml 3 neckflask equipped with a mechanical top stirrer, thermometer and a refluxcondenser was heated at reflux (˜68° C.) with stirring for 2 hours. Next67.6 g (1 eq) of polydextrose that had been dried in the vacuum ovenovernight at 80° C. and 1 g potassium carbonate were added and theheating was continued. Next the methanol removal was started. Thetemperature remained at 68° C. for about 1 hour and then the reactionmixture began to thicken and the temperature rose to 155° C. The mixturewas very thick at this temperature and the mixture solidified uponcooling. After cooling, 118.8 g of a brittle black solid remained whichhad a hydroxyl value of 591. The solid was not completely soluble inwater but slightly soluble in methanol and THF and mostly soluble inmethoxyethanol.

EXAMPLE 14

Polydextrose Ester—Reaction of Polydextrose with Acid Chlorides

Example 14A

(Theoretical Level of OH Replacement ˜10%)

200 g DMF, 10 g (0.126 eq) pyridine and 33.8 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 9.5 g (0.05 eq) ofdecanoyl chloride was added dropwise over a 1.5 hour period and duringthe addition, the temperature rose to 90° C. but dropped back to 84° C.at the end of this period.

Small aliquots were removed and mixed with different solvents with thefollowing results:

-   -   water—no precipitate    -   ethanol—slight precipitate    -   acetone—white precipitate that is soluble in water    -   methanol—no precipitate

The DMF was distilled off under vacuum (temp rose to 95° C. during thedistillation). 55.7 g of a gummy residue was left which was washed with300 ml of ethanol. The solid was filtered leaving about 38.6 g of “wet”product. After vacuum drying, 21.8 g (53%) of product remained which hada hydroxyl value of 725.

Example 14B

(Theoretical Level of Hydroxyl Replacement ˜30%)

200 g DMF, 15.8 g (0.2 eq) pyridine and 34 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 28.6 g (0.15 eq) ofdecanoyl chloride was added dropwise over a 1.0 hour period and duringthe addition, the temperature rose to 90° C. but dropped back to 85° C.at the end of this period.

Next 300 ml of water was added leading to a gummy precipitate. Aftercooling the water was decanted away and the gummy solid was washed 2times with 200 ml of water. The water was decanted away and the gummysolid placed in a vacuum oven at 70° C. and dried. 46.1 g of productresulted (˜81%) yield) which had a hydroxyl value of 427.

Example 14C

(Theoretical Level of Hydroxyl Replacement ˜40%)

200 g DMF, 19.75 g (0.25 eq) pyridine and 34 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 38.1 g (0.2 eq) ofdecanoyl chloride was added dropwise over a 0.75 hour period and duringthe addition, the temperature rose to 91° C.

Next 400 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 200 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 60.13g of product resulted (˜140% yield). Apparently, the by-product pyridinehydrochloride was trapped in with the product. The product was washedagain with water and dried but still most of the pyridine hydrochlorideremained. The solid was then mixed with water and heated to 60° C. andthe stickiness seemed to go away. It was filtered and washed againfiltered and dried under vacuum. 52.3 g of product resulted (80.7%yield) which had a hydroxyl value of 372.

Example 14D

(Theoretical Level of Hydroxyl Replacement ˜15%)

200 g DMF, 7.9 g (0.1 eq) pyridine and 34 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 14.3 g (0.075 eq) ofdecanoyl chloride was added dropwise over a 0.75 hour period and duringthe addition, the temperature rose to 95° C. An aliquot was removed andwater was added—very little precipitate. Similarly when ethanol wasadded no precipitate resulted. Since the product does not precipitatereadily, the DMF was distilled off under vacuum, keeping the pottemperature below 100° C. during the distillation.

Next 300 ml of acetone was added to the residue. The insoluble materialwas gummy and difficult to work with. It was also still veryhydroscopic. The solid was filtered and dried in the vacuum oven, 38.95g of solid was obtained which had a hydroxyl value of 483.

Example 14E

(Theoretical Level of Hydroxyl Replacement ˜20%)

200 g DMF, 9.5 g (0.12 eq) pyridine and 34 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 19.05 g (0.10 eq) ofdecanoyl chloride was added dropwise over a 2 hour period and during theaddition, the temperature rose to 90° C.

Next 500 ml of water was added and the mixture was cooled in therefrigerator. The liquid was decanted away from the gummy solids andmore water (200 ml) was added to wash the product further. The water wasdecanted away from the gummy solids. The solids were dried in the vacuumoven overnight at 70° C. 27.95 g solids resulted (˜56.6%) yield) whichhad a hydroxyl value of 529.

Example 14F

(Theoretical Level of Hydroxyl Replacement ˜30%)

200 g DMF, 15.8 g (0.2 eq) pyridine and 34 g (0.5 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 29.2 g (0.15 eq) ofdecanoyl chloride was added dropwise over a 0.25 hour period and duringthe addition, the temperature rose to 90° C. and heat applied andcontinued at 90° C. for an additional 2 hours.

Next 300 ml of water was added leading to a gummy precipitate. Aftercooling the water was decanted away and the gummy solid was washed 2times with 200 ml of water. The water was decanted away and the gummysolid placed in a vacuum oven at 70° C. and dried. 50.1 g of productresulted (˜87%) yield) which had a hydroxyl value of 434.

Example 14G

(Theoretical Level of Hydroxyl Replacement ˜40%)

200 g DMF, 39.5 g (0.5 eq) pyridine and 68 g (1.0 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 76.2 g (0.4 eq) ofdecanoyl chloride was added dropwise over 15 minutes and next themixture was to 90° C. and held there for 1 hour.

Next 800 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 400 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 121.7g of product resulted (˜94% yield) which had a hydroxyl value of 333.

Example 14H

(Theoretical Level of Hydroxyl Replacement ˜40%)

400 g DMF, 39.5 g (0.5 eq) pyridine and 68 g (1.0 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 65.1 g (0.4 eq) ofoctanoyl chloride was added dropwise over 15 minutes and next themixture was to 90° C. and held there for 1 hour.

Next 800 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 400 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 91.7 gof product resulted (˜77% yield) which had a hydroxyl value of 366.

Example 14I

(Theoretical Level of Hydroxyl Replacement ˜40%)

400 g DMF, 39.5 g (0.5 eq) pyridine and 68 g (1.0 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 65.1 g (0.4 eq) ofisooctanoyl chloride was added dropwise over 15 minutes and next themixture was to 90° C. and held there for 1 hour.

Next 800 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 400 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 74.6 gof product resulted (˜63% yield) which had a hydroxyl value of 333.

Example 14J

(Theoretical Level of Hydroxyl Replacement ˜60%)

400 g DMF, 55.4 g (0.7 eq) pyridine and 68 g (1.0 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 65.1 g (0.4 eq) ofoctanoyl chloride was added dropwise over 15 minutes and next themixture was to 90° C. and held there for 1 hour.

Next 800 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 400 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 135.5g of product resulted (˜94.3% yield) which had a hydroxyl value of 258.

Example 14K

(Theoretical Level of Hydroxyl Replacement ˜60%)

400 g DMF, 55.4 g (0.7 eq) pyridine and 68 g (1.0 eq) of polydextrose(vacuum dried overnight at 80° C.) was placed in a 1 liter 4 neckedflask equipped with a top mechanical stirrer, reflux condenser and anadditional funnel. The mixture was heated to 70° C. and during that timeall of the polydextrose went into solution. Next 114.4 g (0.6 eq) ofdecanoyl chloride was added dropwise over 15 minutes and next themixture was to 90° C. and held there for 1 hour.

Next 800 ml of water was added leading to a gummy precipitate. Aftercooling in a freezer, the water was decanted away and the gummy solidwas washed 2 times with 400 ml of water. The water was decanted away andthe dough like solid placed in a vacuum oven at 70° C. and dried. 157.8g of product resulted (˜90.3% yield) which had a hydroxyl value of 229.

EXAMPLE 15

Polydextrose Ester—Reaction of Polydextrose with Vinylneodecanoate

(Theoretical Level of Hydroxyl Replacement ˜50%)

200 g dimethyl sulfoxide (DMSO), 55.4 g (0.7 eq) and 34 g (0.5 eq) ofpolydextrose (vacuum dried overnight at 80° C.) was placed in a 1 liter4 necked flask equipped with a top mechanical stirrer, reflux condenserand an additional funnel. The mixture was heated to 90° C. and then 20 gof sodium bicarbonate was added followed by 29.7 (0.15 equivalents) ofvinyl neodecanoate over 5 minutes and the mixture was heated for 4 hour.No substantial reaction seemed to have occurred (aliquot addition towater with almost no precipitate) so additional sodium bicarbonate (20g) was added followed by an additional 19.1 g (0.1 eq) of vinylneodecanoate. The mixture was gradually heated to 160° C. over a 5 hourperiod.

After cooling, 600 ml of water was added leading to a gummy precipitate.After cooling in a freezer, the water was decanted away and the gummysolid was washed 2 times with 300 ml of water. The water was decantedaway and the dough like solid placed in a vacuum oven at 70° C. anddried. 47.8 g of product resulted (˜66% yield) which had a hydroxylvalue of 319.

EXAMPLE 16

Polydextrose Ether

Example 16A

A mixture of 344 grams of 95DE liquid corn syrup (244 gram anhydrosedextrose), 158 grams of 1-decanol, and 1.2 gm phosphoric acid was heatedunder partial vacuum, with stirring, to remove water and create a hotmelt. The temperature of the mixture was maintained between 152 to 188°C., with stirring, for 5-20 minutes under partial vacuum. Unreacteddecanol forming an oily layer was removed. Upon cooling, approximately262 grams of a brittle substance, being the derivatized, highly branchedpolysaccharide was obtained having 9.2 gm residual unreacted glucose anda hydroxyl value of 674 (equivalent wt=83).

Example 16B

A mixture of 344 grams of 95DE liquid corn syrup (244 gram anhydrosedextrose), 186 grams of 1-dodecanol, and 1.2 gm phosphoric acid washeated under partial vacuum, with stirring, to remove water and create ahot melt. The temperature of the mixture was maintained between 152 to188° C., with stirring, for 5-20 minutes under partial vacuum. Unreacteddecanol forming an oily layer was removed. Upon cooling, approximately235 grams of a brittle substance, being the derivatized, highly branchedpolysaccharide was obtained having 9.2 gm residual unreacted glucose anda hydroxyl value of 687 (equivalent wt=82).

Example 16C

A mixture of 344 grams of 95DE liquid corn syrup (244 gram anhydrosedextrose), 214 grams of 1-tetradecanol, and 1.2 gm phosphoric acid washeated under partial vacuum, with stirring, to remove water and create ahot melt. The temperature of the mixture was maintained between 152 to188° C., with stirring, for 5-20 minutes under partial vacuum. Unreactedtetradecanol forming an oily layer was removed. Upon cooling,approximately 289 grams of a brittle substance, being the derivatized,highly branched polysaccharide was obtained having 12.4 gm residualunreacted glucose and a hydroxyl value of 597 (equivalent wt=94).

Example 16D

A mixture of 344 grams of 95DE liquid corn syrup (244 gram anhydrosedextrose), 214 grams of 1-hexadecanol, and 1.2 gm phosphoric acid washeated under partial vacuum, with stirring, to remove water and create ahot melt. The temperature of the mixture was maintained between 152 to188° C., with stirring, for 5-20 minutes under partial vacuum. Unreactedtetradecanol forming an oily layer was removed. Upon cooling,approximately 274 grams of a brittle substance, being the derivatized,highly branched polysaccharide was obtained having 14.8 gm residualunreacted glucose and a hydroxyl value of 652 (equivalent wt=86).

EXAMPLE 17

Polydextrose Ester Solubility

The solubility of the polydextroses prepared in examples 14 and 15 whereevaluated in different solvents starting with the very polarsolvent—water to the very non polar solvent—methyl t-butyl ether. Thepolarity was reflected by a term known as the solubility parameter (δ),a value which for the very polar water is 23.4° and decreases as onemoves through the Table to the very non polar methyl t-butyl ether, alow number of 7.4. A polymer with a solubility parameter similar to thesolvent will dissolve in it. Components with dramatic differences insolubility parameters, for example water and oil—will not dissolve ormix.

15.0 g of the derivatized highly branched polysaccharide according toExamples 14 and 15 as indicated in Table 2 were added to 85.0 g ofsolvent (15% concentration). The clarity and level of undissolved solidswere noted. The specific solubility parameter of the solvent in whichthe solution was completely clear was recorded as the approximatesolubility of the derivatized highly branched polysaccharide. Ifundissolved solids remained in room temperature (rt) the mixture washeated where after the mix was again noted for any insolubility. TABLE 2Solubility of the Polydextrose Derivatives Solubility 14A 14D 14E 14B14C 15 14F Example No. Parameter 10% 15% 20% 30% 40% 30% 50% Solvent δsub* sub* sub* sub* sub* sub* sub** water 23,4  sol (rt) sol (rt) insolinsol insol insol insol EG 16,3  sol (rt) sol (rt) sl sol part sol partsol (heat) (rt) (rt) methanol 14,5  sol (rt) sol (rt) sol (rt) sol (rt)sol (rt) sol (rt) sol (rt) EG monomethyl 12,1  sol (rt) sol (rt) sol(rt) sol (rt) sol (rt) sol (rt) sol (rt) ether EG monopropyl 11,1  insol sol (heat) sol (rt) sol (rt) sol (rt) sol (rt) sol (rt) ether DPGmonomethyl 10,2  sol (rt) ether acetone 9,9 insol insol sl sol sol (rt)sol (rt) (heat) DPG-n-propyl ether 9,6 sol (rt) DPG-n-butyl ether 9,5insol insol  sol (heat)  sol (heat) sol (rt)  sol (heat) toluene 8,9ethylene dimethyl 8,6 sol (rt) sol (rt) sol (rt) ether MTBE 7,4 insolinsol  sol (heat) sol (rt)  sol (heat) sol (rt)*=acid chloride reaction**=vinyl ester transesterificationEG=ethylene glycolDPG=diproplyleneglycolMTBE=methyl-t-butylether

Table 2 shows how the hydrophilicity decreases and therefore thesolubility in less polar solvents increases as the degree ofsubstitution increases. When more ester groups are introduced thesolubility parameter of the polydextrose derivatives lowered and whenthe solubility parameter is below 14, preferably below. 12 the modifiedpolydextrose dissolved in solvents in which underivatized and lesssubstituted polydextrose is insoluble. Therefore as the substitutionincreased, the polydextrose derivatives became more soluble in the verynon polar solvent, MTBE.

EXAMPLES 18-27

Examples 18-27 illustrate the use of the present derivatized highlybranched polysaccharide or copolymer polyols, in a typical isocyanatebased high resilient (HR) based foam. In each Example, the isocyanatebased foam was prepared by the pre-blending of all resin ingredientsincluding polyols, copolymer polyols (if used), catalysts, water, andsurfactants as well as the derivatized highly branched polysaccharide ofinterest (if used). The isocyanate was excluded from the mixture. Theresin blend and isocyanate were then mixed in a free rise cup at anisocyanate index as indicated in tables 3 and 4 using a high speeddispersator. The foam was allowed to rise freely at room temperature andthe cups were moved to an oven (50° C.) for 1 hour where after theproperties of interest were measured. The methodology will be referredto in Examples 18-27 as the General Procedure.

In Examples 18-27, the following materials are used:

E837, base polyol, commercially available from Lyondell;

E850, a 43% solids content copolymer (SAN) polyol, commerciallyavailable from Lyondell;

D-PDX, polydextrose derivatives produced according to examples 14 C, 14J, 14 K and 15 above;

DEAO LF, diethanol amine, a crosslinking agent commercially availablefrom Air Products; Water, indirect blowing agent;

Dabco 33LV, a gelation catalyst, commercially available from AirProducts;

Niax A-1, a blowing catalyst, commercially available from Witco;

Niax L-3184 a silicon surfactant manufactured by GE

Lupranate T80, isocyanate (toluene diisocyanate—TDI), commerciallyavailable from BASF.

Unless otherwise stated, all parts reported in Examples 18-27 are inparts by weight. In Examples 18-27, isocyanate based foams based on theformulations shown in Table 3 and 4 are produced using the Generalprocedure referred to above. The polydextrose derivatives of Examples22-27 were produced according to Example 14 C (Examples 22 and 23),Example 15 (Examples 24 and 25) and Example 14 J and 14 K (Examples 26and 27).

The results of physical property testing for each foam was the densityand Compressive Load Deflection (CLD) at 50% deflection, measuredpursuant to ASTM D3574 Test C, which is a good screening test for smallfoam samples. The CLD values are given in pounds per square inch (psi).The force in pounds needed to compress the sample was recorded and theresult are reported in psi by dividing the force by the surface area ofthe sample. The CLD determination was run at 50% compression. Sampleswith nominal dimensions of 2″×2″×1″ were prepared. TABLE 3 Control foamsExamples Ingredient 18 A 18 B 19 A 19 B 20 A 20 B 21 A 21 B Hyperlite E863 90 90 80 80 60 60 40 40 Hyperlite E 850 10 10 20 20 40 40 60 60D-PDX DEOA LF 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 water 3.93 3.93 3.93 3.933.93 3.93 3.93 3.93 Dabco 33LV 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33Niax A-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Niax L-3184 1 1 1 1 1 11 1 Total Resin 106.94 106.94 106.94 106.94 106.44 106.44 106.44 106.44TDI 80 46.65 46.65 46.48 46.48 46.13 46.13 45.79 45.79 Index 1.0 1.0 1.01.0 1.0 1.0 1.0 1.0 Mix 5 5 5 5 5 5 5 5 Initiation 10 10 10 10 10 10 1010 Gel 80 80 80 80 80 80 75 75 Rise 80 80 80 80 80 80 75 75 Density(pcf) 1.97 1.99 1.97 2.09 1.73 1.77 1.74 1.80 50% CLD (psi) 0.42 0.410.50 0.53 0.59 0.57 0.75 0.83

In examples 18-21, isocyanate based foams were prepared in the absenceof any derivatized highly branched polysaccharide. Copolymer polyol wasused to increase foam hardness. Thus, it will be appreciated thatExamples 18-21 are provided for comparative purposes only and areoutside the scope of the present invention.

The isocyanate based foams were formulated with a H₂O concentration of3.93% resulting in an approximate foam core density of 1.7-2.09 pcf. Inorder to compare the CLD's of the different foams, one needs to havecomparable densities. Two pairs of polymer polyol controls of Example 18and 19 all have a nominal 2.0 lb/ft³ density. The samples with 20% POP(˜8.6% solids) have a 50% CLD of about 0.52 psi versus 0.41 for the 10%POP (˜4.3% solids). The higher solids POP foams of Example 20 [17.2%]and 21 [25.8%]) show increased 50% CLD (0.58 and 0.79 psi respectively)even at a density slightly below 1.8 lb/ft³. TABLE 4 Examples Ingredient22 A 22 B 23 A 23 B 24 A 24 B 25 A 25 B 26 27 Hyperlite E 863 95 95 9797 95 95 97.5 97.5 95 95 Hyperlite E 850 D-PDX 5 5 3 3 5 5 2.5 2.5 5 5DEOA LE 2.4 2.4 2 2 2 2 2.4 2.4 water 3.93 3.93 3.93 3.93 3.93 3.93 3.933.93 3.93 3.93 Dabco 33LV 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.330.33 Niax A-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Dabcon5164 1 1 1 1 1 1 1 1 Niax 3184 3 3 3 3 1.4 1.4 TDI 80 46.3 46.3 46.046.0 49.2 49.2 49.2 49.2 50.2 50.45 Index 0.86 0.86 0.91 0.91 0.98 0.981.0 1.0 1 1 Mix 5 5 5 5 5 5 5 5 5 5 Initiation 10 10 12 12 10 10 11 14Gel 75 75 75 75 40 40 40 40 60 105 Rise 60 60 75 75 40 40 35 35 75 90Density (pcf) 1.97 1.88 2.27 2.34 2.02 2.24 2.29 2.22 50% CLD (psi) 0.700.57 0.83 0.95 0.66 0.84 0.60 0.31

The Formulation of Example 22 has an average density of 1.95 lb/ft³ andan average 50% CLD of ˜0.64 psi. This CLD is higher than either of thecomparable density POP foams with either 4.3 or 8.6% solids, although asmaller amount of derivatized highly branched polydextrose is used.Similarly the formulation of Example 24 has a slightly higher averagedensity of 2.13 lb/ft³ and an average 50% CLD of 0.75. Another directcomparison of two different polydextrose dendrimers can be made with theformulation of example 24 A and of example 22 A (˜1.97 lb/ft³). Thelower density of the formulation of example 22 A has only a slightlyhigher 50% CLD (0.70 psi) than that of the formulation of example 24 A(0.66 psi).

Moreover, the formulations of example 24B and 25A may be compared sincetheir density is almost the same. The CLD value is lower for 25A whichindicates that the hardness is improved with the increase of the amountof derivatized highly branched polysaccharide.

While this invention has been described with reference to illustrativeembodiments and Examples, the description is not intended to beconstrued in a limiting sense. For example, while esterification/acidderivatisation and ring opening techniques are used in some of theExamples to produce embodiments of the novel derivatized highly branchedpolysaccharide, other derivatisation techniques such astransesterification, polyaddition reactions, free radical polymerisationand the like can be used. Thus, various modifications of theillustrative embodiments, as well as other embodiments of the invention,will be apparent to persons skilled in the art upon reference to thisdescription. It is therefore contemplated that the appended claims willcover any such modifications or embodiments.

All publications, patents and patent applications referred to herein areincorporated by reference in their entirety to the same extent as ifeach individual publication, patent or patent application wasspecifically and individually indicated to be incorporated by referencein its entirety.

1. A highly branched polysaccharide of randomly bonded glucopyranoseunits, having an average number of 10-100 glucose residues wherein saidpolysaccharide has an active hydrogen functionality of at least 15 andis derivatized to provide a hydrophobicity which renders it compatiblewith a polyether polyol with which the underivatized polysaccharide isincompatible.
 2. The highly branched polysaccharide of claim 1, whereinsaid derivatized highly branched polysaccharide has an active hydrogenfunctionality of 15 to
 70. 3. The highly branched polysaccharide ofclaim 2, wherein said derivatized highly branched polysaccharide has anactive hydrogen functionality of 20 to
 60. 4. The highly branchedpolysaccharide of claim 2, wherein said derivatized highly branchedpolysaccharide has an active hydrogen functionality of 30 to
 50. 5. Thehighly branched polysaccharide of claim 1, wherein said derivatizedhighly branched polysaccharide has a solubility parameter below
 14. 6.The highly branched polysaccharide of claim 1, wherein said derivatizedhighly branched polysaccharide has a solubility parameter below
 12. 7.The highly branched polysaccharide of claim 1, wherein saidhydrophobicity of said polysaccharide is sufficient to cause a mixtureof said polysaccharide and said polyether polyol with which theunderivatized polysaccharide is incompatible, said compatibilityindicating mixture comprising at least 5% (w/w) of said polysaccharide,to form a uniform liquid at 23° C.
 8. The highly branched polysaccharideof claim 7, wherein said compatibility indicating mixture comprising 5to 50% of the polysaccharide forms a uniform liquid at 23° C.
 9. Thehighly branched polysaccharide of claim 7, wherein said compatibilityindicating mixture comprising 5 to 40% of the polysaccharide forms auniform liquid at 23° C.
 10. The highly branched polysaccharide of claim7, wherein said compatibility indicating mixture comprising 5 to 30% ofthe polysaccharide forms a uniform liquid at 23° C.
 11. The highlybranched polysaccharide of claim 1, wherein said polysaccharide isderivatized by a chemical reaction with a hydrophobic organic compoundcomprising 6-20 carbon atoms selected from aliphatic and aromatic carbonatoms and combinations thereof.
 12. The highly branched polysaccharideof claim 11, wherein said organic compound is selected from C₆-C₁₂carboxylic acids and C₆-C₁₂ organic alcohols.
 13. The highly branchedpolysaccharide of claim 12, wherein said carboxylic acid is selectedfrom fatty acids or reactive derivatives thereof.
 14. The highlybranched polysaccharide of claim 13, wherein the weight of fatty acidresidues is 5 to 50% based on the weight of the derivatized highlybranched polysaccharide.
 15. The highly branched polysaccharide of claim14, wherein the weight of fatty acid residues is 15 to 40% based on theweight of the derivatized highly branched polysaccharide.
 16. The highlybranched polysaccharide of claim 1, wherein said polyether polyol withwhich the underivatized polysaccharide is incompatible comprises atleast 70% polypropylene oxide.
 17. The highly branched polysaccharide ofclaim 1, wherein said polyether polyol has a hydroxyl value of at most60 mg KOH/g.
 18. The highly branched polysaccharide of claim 17, whereinsaid polyether polyol has a hydroxyl value of 15 to 55 mg KOH/g.
 19. Thehighly branched polysaccharide of claim 17, wherein said polyetherpolyol has a hydroxyl value of 28 to 36 mg KOH/g.
 20. The highlybranched polysaccharide of claim 1, wherein said polyether polyol has amolecular weight in the range of from 200 to 12,000.
 21. The highlybranched polysaccharide of claim 20, wherein said polyether polyol has amolecular weight in the range of from 2,000 to 7,000.
 22. The highlybranched polysaccharide of claim 20, wherein said polyether polyol has amolecular weight in the range of from 2,000 to 6,000.
 23. The highlybranched polysaccharide of claim 1, wherein said highly branchedpolysaccharide consists of randomly cross-linked glucose units with alltypes of glycosidic bonds, containing minor amounts of a bound sugaralcohol and an acid, and having an average molecular weight betweenabout 1,500 and 18,000.
 24. The highly branched polysaccharide of claim23, wherein said highly branched polysaccharide has predominantly 1,6glycosidic bonds.
 25. The highly branched polysaccharide of claim 23,wherein said highly branched polysaccharide is a polycondensationproduct of glucose, maltose or other simple sugars or glucose-containingmaterial such as hydrolyzed starch and a sugar alcohol in the presenceof a carboxylic acid.
 26. The highly branched polysaccharide of claim25, wherein said sugar alcohols are selected from the group consistingof sorbitol, glycerol, erythritol, xylitol, mannitol, galactitol ormixtures thereof, at a level of 5-20% by weight of the underivatizedpolysaccharide.
 27. The highly branched polysaccharide of claim 26,wherein said sugar alcohols are selected from the group consisting ofsorbitol, glycerol, erythritol, xylitol, mannitol, galactitol ormixtures thereof, at a level of 5-15% by weight of the underivatizedpolysaccharide.
 28. The highly branched polysaccharide of claim 26,wherein said sugar alcohols are selected from the group consisting ofsorbitol, glycerol, erythritol, xylitol, mannitol, galactitol ormixtures thereof, at a level of 8-12% by weight of the underivatizedpolysaccharide.
 29. The highly branched polysaccharide of claim 26,wherein said polysaccharide is a polycondensation product of glucose,sorbitol and citric acid.
 30. The highly branched polysaccharide ofclaim 26, wherein said polysaccharide is a polydextrose.
 31. The highlybranched polysaccharide of claim 23, wherein said polysaccharide ispurified by a process selected from fractionation, extraction,neutralization, purification by chromatography, filtration, enzymetreatment, carbon treatment and hydrogenation.
 32. The highly branchedpolysaccharide of claim 1, wherein said polysaccharide has predominantlybeta-1,4 linkages and a varying number of glucose residues which arehydrolysed from starch to form dextrins and subsequently linked to formbranched structures.
 33. The highly branched polysaccharide of claim 32,wherein said polysaccharide is pyroconverted starch.
 34. The highlybranched polysaccharide of claim 1, wherein said polysaccharide is apolydextrose having an active hydrogen functionality of at least 15,derivatized with a C₈₋₁₂-fatty acid to provide a hydrophobicity whichrenders it compatible with a polyether polyol with which theunderivatized polydextrose is incompatible.
 35. A mix for the productionof a polyurethane comprising a mixture of a polyether polyol and ahighly branched polysaccharide of randomly bonded glucopyranose units,having an average number of 10-100 glucose residues, wherein saidpolysaccharide has an active hydrogen functionality of at least 15 andis derivatized to provide a hydrophobicity which renders it compatiblewith said polyether polyol with which the underivatized polysaccharideis incompatible.
 36. The mix of claim 35, wherein said polyurethane isflexible polyurethane foam.
 37. The mix of claim 35, wherein said mixcomprises 1 to 50% by weight of said polysaccharide.
 38. The mix ofclaim 37, wherein said mix comprises 5 to 20% by weight of saidpolysaccharide.
 39. The mix of claim 37, wherein said mix comprises 10to 15% by weight of said polysaccharide.
 40. The mix of claim 35,wherein said derivatized highly branched polysaccharide has an activehydrogen functionality of 15 to
 70. 41. The mix of claim 40, whereinsaid derivatized highly branched polysaccharide has an active hydrogenfunctionality of 20 to
 60. 42. The mix of claim 40, wherein saidderivatized highly branched polysaccharide has an active hydrogenfunctionality of 30 to
 50. 43. The mix of claim 35, wherein saidderivatized highly branched polysaccharide has a solubility parameterbelow
 14. 44. The mix of claim 35, wherein said derivatized highlybranched polysaccharide has a solubility parameter below
 12. 45. The mixof claim 35, wherein said hydrophobicity of said polysaccharide issufficient to cause a mixture of said polysaccharide and said polyetherpolyol with which the underivatized polysaccharide is incompatible, saidcompatibility indicating mixture comprising at least 5% (w/w) of saidpolysaccharide to form a uniform liquid at 23° C.
 46. The mix of claim45, wherein said compatibility indicating mixture comprising 5 to 50% ofthe polysaccharide forms a uniform liquid at 23° C.
 47. The mix of claim46, wherein said compatibility indicating mixture comprising 5 to 40% ofthe polysaccharide forms a uniform liquid at 23° C.
 48. The mix of claim46, wherein said compatibility indicating mixture comprising 5 to 30% ofthe polysaccharide forms a uniform liquid at 23° C.
 49. The mix of claim35, wherein said polysaccharide is derivatized by a chemical reactionwith an organic compound comprising 6-20 carbon atoms selected fromaliphatic aromatic carbon atoms and combinations thereof.
 50. The mix ofclaim 49, wherein said organic compound is selected from the groupconsisting of C₆-C₁₂ carboxylic acids and C₆-C₁₂ organic alcohols. 51.The mix of claim 50, wherein said carboxylic acid is selected from thegroup consisting of fatty acids or reactive derivatives thereof.
 52. Themix of claim 51 wherein the weight of fatty acid residues is 5 to 50%based on the weight of the derivatized highly branched polysaccharide.53. The mix of claim 52, wherein the weight of fatty acid residues is 15to 40% based on the weight of the derivatized highly branchedpolysaccharide.
 54. The mix of claim 35, wherein said polyether polyolwith which the underivatized polysaccharide is incompatible comprises atleast 70% polypropylene oxide.
 55. The mix of claim 35, wherein saidpolyether polyol has a hydroxyl value of at most 60 mg KOH/g.
 56. Themix of claim 55, wherein said polyether polyol has a hydroxyl value of15 to 55 mg KOH/g.
 57. The mix of claim 55, wherein said polyetherpolyol has a hydroxyl value of 28 to 36 mg KOH/g
 58. The mix of claim35, wherein said polyether polyol has a molecular weight in the range offrom 200 to 12,000.
 59. The mix of claim 58, wherein said polyetherpolyol has a molecular weight in the range of from 2,000 to 7,000. 60.The mix of claim 35, wherein said mix further comprises at least onecatalyst and at least one surfactant.
 61. The mix of claim 60, whereinsaid catalyst is selected from the group consisting of tertiary amines,metallic salts and mixtures thereof.
 62. The mix of claim 60, Whereinsaid surfactant is a silicone surfactant.
 63. The mix of claim 35,wherein said mix further comprises at least one blowing agent selectedfrom the group consisting of water, non-water blowing agents, liquidcarbon dioxide and combinations thereof.
 64. The mix of claim 63,wherein said blowing agent is water.
 65. The mix of claim 63, whereinsaid blowing agent is a low-boiling organic liquid.
 66. The mix of claim35, wherein said polysaccharide is a polydextrose having an activehydrogen functionality of at least 15, derivatized with a C₈₋₁₂-fattyacid to provide a hydrophobicity which renders it compatible with apolyether polyol with which the underivatized polydextrose isincompatible.